CN109181024A

CN109181024A - Utilize the native rubber composite material and preparation method of wastewaters with modified calcium sulfate whiskers preparation

Info

Publication number: CN109181024A
Application number: CN201810942595.0A
Authority: CN
Inventors: 杨眉; 王家琛
Original assignee: China University of Geosciences Wuhan
Current assignee: China University of Geosciences Wuhan
Priority date: 2018-08-17
Filing date: 2018-08-17
Publication date: 2019-01-11

Abstract

The present invention provides a kind of native rubber composite material prepared using wastewaters with modified calcium sulfate whiskers, is made by following raw material: wastewaters with modified calcium sulfate whiskers, natural rubber, accelerant CZ, zinc oxide, stearic acid and sulphur.The present invention also provides a kind of preparation methods of native rubber composite material using wastewaters with modified calcium sulfate whiskers preparation, steps are as follows: wastewaters with modified calcium sulfate whiskers being added in natural rubber, acetum is then continuously added, stirs while adding, until natural rubber solidifies, solid rubber is obtained；Benefit is rinsed with water solution of the solid rubber after rinsing and is in neutrality, and then dries solid rubber；Solid rubber after accelerant CZ and drying is placed on opening rubber mixing machine and is kneaded, zinc oxide, stearic acid and sulfur cross-linking is added then to get native rubber composite material is arrived.Preparation method of the invention effectively increases the compatibility of calcium sulfate crystal whiskers and organic polymer matrix.

Description

Utilize the native rubber composite material and preparation method of wastewaters with modified calcium sulfate whiskers preparation

Technical field

The present invention relates to technical field of rubber material more particularly to a kind of natural rubbers prepared using wastewaters with modified calcium sulfate whiskers Glue composite material and preparation method.

Background technique

What most widely used, technology was the most mature in existing gum filler is carbon black and calcium sulfate, magnesium sulfate etc. Inorganic filler, but these material constructions are expensive, so that the rubber composite material cost of preparation increases.

Calcium sulfate crystal whiskers are using cheap gypsum as raw material, by artificially controlling, with single crystal form growth, tool There is the fibrous crystal of uniform cross section, complete shape, perfect internal structure.It may be used as the enhancing group of material Point, compared with glass fibre, calcium sulfate crystal whiskers have more tiny, high temperature resistant, good toughness, intensity high, poly- with rubber and plastics etc. The advantages that affinity of conjunction object is stronger, can be widely applied in the industries such as plastics, rubber, papermaking, adhesive.But by sulphur When sour calcium pyroborate is applied to prepare rubber, since calcium sulfate crystal whiskers are inorganic matters, surface is in strong hydrophilicity oleophobic property, is gathered with organic It is poor to close object matrix compatibility, causes reinforcing effect undesirable.Rubber is prepared using calcium sulfate crystal whiskers using traditional mechanical blending method When glue composite material, rubber phase and calcium sulfate crystal whiskers cannot be sufficiently mixed, and the mechanical property of rubber is caused to be affected.

Summary of the invention

In view of this, the present invention provides a kind of mechanical properties with higher to utilize wastewaters with modified calcium sulfate whiskers preparation Native rubber composite material additionally provides a kind of preparation side of native rubber composite material using wastewaters with modified calcium sulfate whiskers preparation Method, the preparation method is low in cost, simple process, substantially increases the compatibility of calcium sulfate crystal whiskers and organic polymer matrix.

The present invention provides a kind of native rubber composite material prepared using wastewaters with modified calcium sulfate whiskers, by following raw material system : wastewaters with modified calcium sulfate whiskers, natural rubber, accelerant CZ, zinc oxide, stearic acid and sulphur.

Further, it is made: 30 parts of wastewaters with modified calcium sulfate whiskers, 100 parts of natural rubber, being promoted by the raw material of following mass parts 2 parts of agent CZ, 5 parts of zinc oxide, 2 parts of stearic acid, 2.5 parts of sulphur；The accelerant CZ is N- cyclohexyl -2-[4-morpholinodithio time sulphur Amide.

Further, the wastewaters with modified calcium sulfate whiskers is made by following raw material: dehydrated alcohol, silane coupling agent and calcium sulfate Whisker.

Further, the wastewaters with modified calcium sulfate whiskers is made by following raw material: aluminate coupling agent, stearic acid and calcium sulfate Whisker.

The present invention also provides a kind of preparation sides of above-mentioned native rubber composite material using wastewaters with modified calcium sulfate whiskers preparation Method, comprising the following steps:

Wastewaters with modified calcium sulfate whiskers is added in natural rubber by S1, is then continuously added acetum, it is molten that acetic acid is added in side The stirring of liquid side obtains solid rubber until natural rubber solidifies；

Then S2 is dried solid rubber using water repeated flushing solid rubber until the solution after rinsing is in neutrality；

Solid rubber after accelerant CZ and drying is placed on opening rubber mixing machine and is kneaded, oxidation is then added by S3 Zinc, stearic acid and sulfur cross-linking to get arrive native rubber composite material.

Further, the preparation process of the wastewaters with modified calcium sulfate whiskers are as follows: weigh water, dehydrated alcohol and silane coupling agent and exist Hydrolyze 2min at 55~70 DEG C, obtain hydrolyzate, the hydrolyzate is uniformly sprayed on to the surface of calcium sulfate crystal whiskers, then 30~ Calcium sulfate crystal whiskers are dried at 50 DEG C, then stir 6~15min at 100~120 DEG C to get wastewaters with modified calcium sulfate whiskers is arrived.

Further, the water, dehydrated alcohol, silane coupling agent volume ratio be 1:18:1, the silane coupling agent Dosage is the 3%~7% of calcium sulfate crystal whiskers quality.

Further, the preparation process of the wastewaters with modified calcium sulfate whiskers are as follows: calcium sulfate crystal whiskers are added in blender, so Divide 3min to be added in blender aluminate coupling agent afterwards, stearic acid the reaction was continued 10~25min is added after reacting 6min, i.e., Obtain wastewaters with modified calcium sulfate whiskers.

Further, in reaction process, the revolving speed of blender is set as 1200 revs/min, and temperature setting is 100~120 DEG C, The dosage of the aluminate coupling agent is the 1%~3% of calcium sulfate crystal whiskers quality, and the stearic dosage is calcium sulfate crystal whiskers The 0.5%~2% of quality.

Further, in step S1, the mass ratio of acetic acid and water is 1:20 in the acetum；In step S2, solid The drying temperature of rubber is 30~50 DEG C；In step S3, the time of mixing is 5~10min, and the time of vulcanization is 6~8min.

Technical solution provided by the invention has the benefit that preparation method provided by the invention by by calcium sulfate Whisker is modified, and is then replaced traditional gum filler carbon black using wastewaters with modified calcium sulfate whiskers, is greatly reduced filler cost, Filler cost can reduce by 4 times or more, and since the raw material of calcium sulfate crystal whiskers are the solid waste phosphorus stone of sulfuric acid industry Cream, and then substantially increase the utilization rate of desulfurization；Method provided by the invention uses emulsion blending coagulation method system Standby rubber composite material, compared with traditional mechanical blending method, simple process effectively increases calcium sulfate crystal whiskers and organic polymer The compatibility of object matrix, every mechanical property of rubber composite material obtained are superior to the rubber composite material of addition carbon black.

Detailed description of the invention

Fig. 1 is a kind of stream of the preparation method of the native rubber composite material using wastewaters with modified calcium sulfate whiskers preparation of the present invention Journey schematic diagram.

Specific embodiment

To make the object, technical solutions and advantages of the present invention clearer, below in conjunction with attached drawing to embodiment party of the present invention Formula is further described.

The embodiment provides it is a kind of using wastewaters with modified calcium sulfate whiskers prepare native rubber composite material, by with Lower raw material is made: wastewaters with modified calcium sulfate whiskers, natural rubber, accelerant CZ, zinc oxide, stearic acid and sulphur.

Specifically, the native rubber composite material that the embodiment of the present invention provides is made by the raw material of following mass parts: being changed 30 parts of calcium sulfate crystal whiskers, 100 parts of natural rubber, 2 parts of accelerant CZ, 5 parts of zinc oxide, 2 parts of stearic acid, 2.5 parts of sulphur of property；Its In, accelerant CZ is N- cyclohexyl -2-[4-morpholinodithio sulfenamide, and appearance is in canescence or pale yellow powder.

Wastewaters with modified calcium sulfate whiskers is prepared using two methods in the embodiment of the present invention:

The first preparation method of wastewaters with modified calcium sulfate whiskers is to utilize dehydrated alcohol, silane coupling agent and calcium sulfate crystal whiskers system Standby wastewaters with modified calcium sulfate whiskers, specific preparation process are as follows: weigh the temperature strip of water, dehydrated alcohol and silane coupling agent at 55~70 DEG C 2min is hydrolyzed under part, obtains hydrolyzate, hydrolyzate is uniformly sprayed on to the surface of calcium sulfate crystal whiskers, then in 30~50 DEG C of temperature Under the conditions of calcium sulfate crystal whiskers are dried, then stir 6 under the conditions of 100~120 DEG C of temperature with 1000~1500 revs/min of revolving speed ~15min to get arrive wastewaters with modified calcium sulfate whiskers, wherein in preparation process, water, dehydrated alcohol, silane coupling agent volume ratio be 1:18:1, the dosage of silane coupling agent are the 3%~7% of calcium sulfate crystal whiskers quality, and silane coupling agent selects silane coupling agent KH- 560, silane coupling agent KH-560 are the abbreviations of γ-(2,3- the third oxygen of epoxy) propyl trimethoxy silicane, and No. CAS is 2530- 83-8。

Second of preparation method of wastewaters with modified calcium sulfate whiskers is to utilize aluminate coupling agent, stearic acid and calcium sulfate crystal whiskers system Standby wastewaters with modified calcium sulfate whiskers, specific preparation process are as follows: calcium sulfate crystal whiskers are added in blender, then by aluminate coupling agent Point 3min is added in blender, is reacted and is added stearic acid after 6min the reaction was continued 10~25min to get brilliant to modified calcium sulfate Must, in reaction process, the revolving speed of blender is set as 1200 revs/min, and temperature setting is 100~120 DEG C, aluminate coupling agent Dosage is the 1%~3% of calcium sulfate crystal whiskers quality, and stearic dosage is the 0.5%~2% of calcium sulfate crystal whiskers quality.

Referring to FIG. 1, the embodiments of the present invention also provide the preparation methods of above-mentioned native rubber composite material, including with Lower step:

30 parts of wastewaters with modified calcium sulfate whiskers are added in the natural rubber of 100 parts of liquid, so by step S1 in parts by mass After be continuously added acetum, kept stirring when acetum is added, until natural rubber solidify, obtain solid rubber；Vinegar The mass ratio of acetic acid and water is 1:20 in acid solution, and the effect of acetum is to solidify the natural rubber of liquid.

Then step S2 is existed solid rubber using water repeated flushing solid rubber until the solution after rinsing is in neutrality It is dried under the conditions of 30~50 DEG C of temperature；

Step S3, in parts by mass, by after drying solid rubber and 2 parts of accelerant CZs be placed on opening rubber mixing machine It is kneaded 5~10min, 5 parts of zinc oxide, 2 parts of stearic acid and 2.5 parts of 6~8min of sulfur cross-linking are added then to get natural rubber is arrived Composite material.

Native rubber composite material provided by the invention and preparation method thereof is described in detail below with reference to embodiment:

Embodiment 1:

It weighs water, dehydrated alcohol and silane coupling agent KH-560 and hydrolyzes 2min at 65 DEG C, hydrolyzate is obtained, by hydrolyzate It is uniformly sprayed on the surface of calcium sulfate crystal whiskers, then dries calcium sulfate crystal whiskers at 45 DEG C, recycles miniature high-speed blender will Calcium sulfate crystal whiskers after drying at 105 DEG C with 1200 revs/min of revolving speed stirring 8min to get arriving wastewaters with modified calcium sulfate whiskers, In, water, dehydrated alcohol, silane coupling agent KH-560 volume ratio be 1:18:1, the dosage of silane coupling agent KH-560 is sulfuric acid The 5% of calcium pyroborate quality；36g wastewaters with modified calcium sulfate whiskers is added in 120g natural rubber, acetum is then continuously added, It is kept stirring when acetum is added, until natural rubber solidifies, obtains solid rubber, the matter of acetic acid and water in acetum Amount is than being 1:20；Using water repeated flushing solid rubber until the solution after rinsing is in neutrality, then solid rubber is placed in It is dried at 45 DEG C in baking oven；By after drying solid rubber and 2.4g accelerant CZ be placed on opening rubber mixing machine and be kneaded Then 6min is added 6g zinc oxide, 2.4g stearic acid and 3g sulfur cross-linking 4 and divides 43 seconds to get native rubber composite material is arrived.

Mechanics Performance Testing, natural rubber made from embodiment 1 are carried out to native rubber composite material made from embodiment 1 The shore hardness of composite material is 53.5, and tearing strength 48.64kN/m, fracture tensile strength 22.155%, 300% stretches surely Stress is 5.28MPa, and tearing elongation is 522.43%.

In embodiment 1, every 1.2g is portion.

Embodiment 2:

In order to further illustrate wastewaters with modified calcium sulfate whiskers made from embodiment 1 to the shadow of native rubber composite material performance It rings, the present invention on the basis of embodiment 1, has carried out parallel laboratory test, and carry out to each native rubber composite material obtained Mechanics Performance Testing, the results are shown in Table 1 for parallel laboratory test, in table 1, during preparing native rubber composite material, and sample Product number be 0 experiment in use be 20 mass parts unmodified calcium sulfate crystal whiskers, sample number into spectrum be K10 experiment in plus Enter wastewaters with modified calcium sulfate whiskers made from the embodiment 1 of 10 mass parts, the reality of 15 mass parts is added in the experiment that sample number into spectrum is K15 Wastewaters with modified calcium sulfate whiskers made from example 1 is applied, is added made from the embodiment 1 of 20 mass parts and changes in the experiment that sample number into spectrum is K20 Property calcium sulfate crystal whiskers, sample number into spectrum be K30 experiment in wastewaters with modified calcium sulfate whiskers made from the embodiment 1 of 30 mass parts is added, Wastewaters with modified calcium sulfate whiskers made from the embodiment 1 of 15 mass parts and 15 mass parts is added in the experiment that sample number into spectrum is 15L+15C Carbon black；Other processes for preparing native rubber composite material of embodiment 2 and other raw materials are same as Example 1.

As shown in Table 1, the resultant force of native rubber composite material made from the wastewaters with modified calcium sulfate whiskers using 30 mass parts It is best to learn performance, high mechanical properties of the mechanical property than native rubber composite material made from doping carbon black.

The mechanical property of native rubber composite material made from the different wastewaters with modified calcium sulfate whiskers dosages of table 1

Embodiment 3:

Calcium sulfate crystal whiskers are added in miniature high-speed blender, then divide 3min to be added aluminate coupling agent DL-411 Into blender, reacts and stearic acid the reaction was continued 15min is added after 6min to get wastewaters with modified calcium sulfate whiskers is arrived, in reaction process, The revolving speed of miniature high-speed blender is set as 1200 revs/min, and temperature setting is 105 DEG C, the dosage of aluminate coupling agent DL-411 It is the 2.5% of calcium sulfate crystal whiskers quality, stearic dosage is the 2% of calcium sulfate crystal whiskers quality；By 36g wastewaters with modified calcium sulfate whiskers It is added in 120g natural rubber, is then continuously added acetum, is kept stirring when acetum is added, until natural rubber Solidification, obtains solid rubber, and the mass ratio of acetic acid and water is 1:20 in acetum；Using water repeated flushing solid rubber until Solution after flushing is in neutrality, and then solid rubber is placed in baking oven and is dried at 45 DEG C；By the solid rubber after drying It is placed on opening rubber mixing machine with 2.4g accelerant CZ and is kneaded 6min, 6g zinc oxide, 2.4g stearic acid and 3g sulphur is then added Sulphur vulcanize 5 points 07 second to get arrive native rubber composite material.

In embodiment 3, every 1.2g is portion.

Then preparation method provided by the invention is taken by being modified calcium sulfate crystal whiskers using wastewaters with modified calcium sulfate whiskers For traditional gum filler carbon black, filler cost is greatly reduced, filler cost can reduce by 4 times or more, and due to sulfuric acid The raw material of calcium pyroborate are the solid waste phosphogypsum of sulfuric acid industry, and then substantially increase the utilization of desulfurization Rate；Method provided by the invention prepares rubber composite material using emulsion blending coagulation method, compared with traditional mechanical blending method, Simple process, effectively increases the compatibility of calcium sulfate crystal whiskers and organic polymer matrix, rubber composite material obtained it is each Item mechanical property is superior to the rubber composite material of addition carbon black.

In the absence of conflict, the feature in embodiment and embodiment herein-above set forth can be combined with each other.

The foregoing is merely presently preferred embodiments of the present invention, is not intended to limit the invention, it is all in spirit of the invention and Within principle, any modification, equivalent replacement, improvement and so on be should all be included in the protection scope of the present invention.

Claims

1. a natural rubber composite material utilizing modified calcium sulfate whisker to prepare, is characterized in that, is made by following raw material: modified calcium sulfate whisker, natural rubber, accelerator CZ, zinc oxide, stearic acid and sulfur .

2. the natural rubber composite material utilizing modified calcium sulfate whiskers to prepare according to claim 1, is characterized in that, obtained by the raw material of following mass parts: 30 parts of modified calcium sulfate whiskers, 100 parts of natural rubber, 2 parts of accelerator CZ, 5 parts of zinc oxide, 2 parts of stearic acid, 2.5 parts of sulfur; the accelerator CZ is N-cyclohexyl-2-benzothiazole sulfenamide.

3. the natural rubber composite material utilizing modified calcium sulfate whisker to prepare according to claim 1 and 2, is characterized in that, described modified calcium sulfate whisker is made from following raw material: dehydrated alcohol, silane coupling agent and calcium sulfate whiskers.

4. the natural rubber composite material utilizing modified calcium sulfate whisker to prepare according to claim 1 and 2, is characterized in that, described modified calcium sulfate whisker is made from following raw material: aluminate coupling agent, Stearic acid and calcium sulfate whiskers.

5. the preparation method of the natural rubber composite material utilizing modified calcium sulfate whisker to prepare according to any one of claim 1 or 2, is characterized in that, comprises the following steps:

S1, adding the modified calcium sulfate crystal whiskers into the natural rubber, then continuously adding the acetic acid solution, stirring while adding the acetic acid solution, until the natural rubber is solidified to obtain solid rubber;

S2, use water to rinse the solid rubber repeatedly until the solution after the rinse is neutral, and then dry the solid rubber;

S3, the accelerator CZ and the dried solid rubber are placed on an open rubber mixer for mixing, and then zinc oxide, stearic acid and sulfur are added for vulcanization to obtain a natural rubber composite material.

6. the preparation method of the natural rubber composite material utilizing modified calcium sulfate crystal whisker to prepare as claimed in claim 5, is characterized in that, the preparation process of described modified calcium sulfate crystal whisker is: take by weighing water, dehydrated alcohol and The silane coupling agent is hydrolyzed at 55 to 70 ° C for 2 minutes to obtain a hydrolyzed solution. The hydrolyzed solution is sprayed evenly on the surface of the calcium sulfate whiskers, and then the calcium sulfate whiskers are dried at 30 to 50 ° C. The modified calcium sulfate whiskers are obtained by stirring for 6 to 15 minutes at ~120°C.

7. the preparation method of the natural rubber composite material utilizing modified calcium sulfate whisker preparation as claimed in claim 6, is characterized in that, the volume ratio of described water, dehydrated alcohol, silane coupling agent is 1:18: 1. The dosage of the silane coupling agent is 3% to 7% of the mass of the calcium sulfate whiskers.

8. the preparation method of the natural rubber composite material utilizing modified calcium sulfate whisker to prepare as claimed in claim 5, is characterized in that, the preparation process of described modified calcium sulfate whisker is: calcium sulfate whisker is added to In the mixer, then the aluminate coupling agent is added to the mixer for 3 minutes, and after 6 minutes of reaction, stearic acid is added to continue the reaction for 10 to 25 minutes to obtain modified calcium sulfate whiskers.

9. the preparation method of the natural rubber composite material utilizing modified calcium sulfate whisker preparation as claimed in claim 8 is characterized in that, in the reaction process, the rotating speed of the mixer is set to 1200 rev/min, and the temperature is set to 100～120 ℃, the dosage of the aluminate coupling agent is 1% to 3% of the mass of the calcium sulfate whiskers, and the dosage of the stearic acid is 0.5% to 2% of the mass of the calcium sulfate whiskers.

10. the preparation method of the natural rubber composite material utilizing modified calcium sulfate whisker to prepare as claimed in claim 5, is characterized in that, in step S1, in described acetic acid solution, the mass ratio of acetic acid and water is 1:20; In step S2, the drying temperature of the solid rubber is 30-50°C; in step S3, the mixing time is 5-10 min, and the vulcanization time is 6-8 min.